CN111632575A - Composite adsorbent and preparation method thereof - Google Patents
Composite adsorbent and preparation method thereof Download PDFInfo
- Publication number
- CN111632575A CN111632575A CN202010126660.XA CN202010126660A CN111632575A CN 111632575 A CN111632575 A CN 111632575A CN 202010126660 A CN202010126660 A CN 202010126660A CN 111632575 A CN111632575 A CN 111632575A
- Authority
- CN
- China
- Prior art keywords
- zeolite
- activated carbon
- composition
- geopolymer
- mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003463 adsorbent Substances 0.000 title claims abstract description 107
- 239000002131 composite material Substances 0.000 title claims abstract description 100
- 238000002360 preparation method Methods 0.000 title description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 190
- 239000000203 mixture Substances 0.000 claims abstract description 145
- 239000010457 zeolite Substances 0.000 claims abstract description 97
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 96
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 81
- 239000000463 material Substances 0.000 claims abstract description 81
- 229920000876 geopolymer Polymers 0.000 claims abstract description 62
- 238000001179 sorption measurement Methods 0.000 claims abstract description 53
- 239000003513 alkali Substances 0.000 claims abstract description 50
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 49
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 25
- 239000007787 solid Substances 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 238000007493 shaping process Methods 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 75
- 239000012190 activator Substances 0.000 claims description 59
- 238000000034 method Methods 0.000 claims description 58
- 230000008569 process Effects 0.000 claims description 29
- 239000008188 pellet Substances 0.000 claims description 21
- 239000002023 wood Substances 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 18
- 238000011065 in-situ storage Methods 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000002028 Biomass Substances 0.000 claims description 10
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 9
- 238000001125 extrusion Methods 0.000 claims description 9
- 238000005469 granulation Methods 0.000 claims description 8
- 230000003179 granulation Effects 0.000 claims description 8
- 239000002699 waste material Substances 0.000 claims description 8
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims description 7
- 239000003245 coal Substances 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 230000003213 activating effect Effects 0.000 claims description 6
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims description 6
- 239000003610 charcoal Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000002585 base Substances 0.000 claims description 4
- 239000012530 fluid Substances 0.000 claims description 4
- 229910001387 inorganic aluminate Inorganic materials 0.000 claims description 4
- 229910052909 inorganic silicate Inorganic materials 0.000 claims description 4
- 239000002006 petroleum coke Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 2
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 2
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 2
- 244000060011 Cocos nucifera Species 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 244000082204 Phyllostachys viridis Species 0.000 claims description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 2
- 239000011425 bamboo Substances 0.000 claims description 2
- 229920000592 inorganic polymer Polymers 0.000 claims description 2
- 239000003077 lignite Substances 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000011301 petroleum pitch Substances 0.000 claims 1
- 230000004913 activation Effects 0.000 abstract description 27
- 239000007788 liquid Substances 0.000 abstract description 11
- 239000007789 gas Substances 0.000 abstract description 9
- 239000013543 active substance Substances 0.000 abstract description 7
- 238000000926 separation method Methods 0.000 abstract description 5
- 238000000746 purification Methods 0.000 abstract description 2
- 238000007796 conventional method Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 31
- 238000001994 activation Methods 0.000 description 30
- 235000011121 sodium hydroxide Nutrition 0.000 description 23
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 17
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 13
- 239000004115 Sodium Silicate Substances 0.000 description 13
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 13
- 229910052911 sodium silicate Inorganic materials 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 12
- 239000008187 granular material Substances 0.000 description 11
- 239000000356 contaminant Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 239000000843 powder Substances 0.000 description 9
- 238000012545 processing Methods 0.000 description 9
- 239000002594 sorbent Substances 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 239000010881 fly ash Substances 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 239000003344 environmental pollutant Substances 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 231100000719 pollutant Toxicity 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000011246 composite particle Substances 0.000 description 5
- 238000001027 hydrothermal synthesis Methods 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 235000011837 pasties Nutrition 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- -1 pharmaceutical Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000010426 asphalt Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000011066 ex-situ storage Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 210000001161 mammalian embryo Anatomy 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000518 rheometry Methods 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910052915 alkaline earth metal silicate Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000013211 curve analysis Methods 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000007908 dry granulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 1
- 229910052912 lithium silicate Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 238000006902 nitrogenation reaction Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
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- 239000001301 oxygen Substances 0.000 description 1
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- 239000011591 potassium Substances 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
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- 238000007873 sieving Methods 0.000 description 1
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- 239000002904 solvent Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000005550 wet granulation Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Images
Classifications
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- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
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- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
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- B01J20/165—Natural alumino-silicates, e.g. zeolites
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- B01J20/2803—Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
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Abstract
A composition for making a composite adsorbent from a mixture of geopolymer, zeolite and activated carbon, wherein the geopolymer material, carbonaceous material and alkaline active agent are components of the mixture. The solids mass ratio of the alkaline active agent to the carbonaceous material is at least 0.25: 1. A process for preparing a shaped composite adsorbent by mixing, shaping, extruding and the like conventional methods using the composition. Alkali activation converts carbonaceous material to activated carbon, followed by hydrothermal treatment to convert geopolymeric material to zeolite. Shaped composite adsorbents made from the compositions of the present invention are useful for adsorption, purification, or other separation applications of liquids and gases.
Description
Technical Field
The invention relates to a composite adsorbent composition and a preparation process thereof. More particularly, the composite adsorbent composition and preparation process involve mixing, shaping, alkali activation and hydrothermal treatment of a mixture of geopolymeric material, carbonaceous material, alkali activator to produce a composite adsorbent comprised of zeolite and activated carbon in a shape and size suitable for adsorption applications.
Background
With the increase of global industrialization, chemical, pharmaceutical, textile, agricultural and many other industries are producing large quantities of harmful pollutants such as heavy metals, organic compounds and pesticides. Since these contaminants pose a serious threat to the environment and health, environmental regulations require their removal from waste streams such as wastewater prior to discharge into the environment or reuse. The adsorption method has the advantages of high efficiency, large adsorption capacity, low operation cost and the like, and is the most ideal method for removing pollutants in wastewater. Zeolites and activated carbon are currently the most widely used pollutant removal adsorbents.
The zeolite is composed of SiO4And AlO4A porous crystalline aluminosilicate having tetrahedra bonded thereto. They have an open structural framework with many channels and interconnecting voids, with pore sizes typically in the range of 0.3-1 nm. These channels are occupied by cations and water molecules. Each AlO in the frame4The tetrahedra all carry a net negative charge balanced by the cations. When the aqueous solution containing ions passes through the pores and voids, the cations can be reversibly exchanged with other ions of the same charge. Therefore, zeolite has excellent adsorption properties for inorganic contaminants such as heavy metals, ammonium, etc., and has a high ion exchange capacity even at concentrations of several parts per million (ppm) or higher.
Zeolites are widely used in a variety of applications, including separation and adsorption processes. In continuous processes for liquid and gas applications, granular zeolites are often used to achieve low pressure drop, ease of operation and regeneration, and long service life. Although zeolites are excellent adsorbents for inorganic contaminants, they are less effective in removing organics, particularly large organics, due to the small pore size of the zeolite (0.3-1 nm) and the hydrophilic nature of most zeolite materials.
Activated carbon, on the other hand, typically has large-sized pores ranging from about one nanometer to several micrometers, and is hydrophobic. Typical activated carbons have a surface area of several hundred square meters per gram and can accumulate a significant amount of contaminant molecules. The activated carbon has the characteristics of large specific surface area, wide pore size distribution and high surface activity, and is very effective in removing organic matters including large aromatic hydrocarbons. However, activated carbon has a lower adsorption efficiency for inorganic contaminants than zeolites and is not generally used for treating waste streams with high concentrations of inorganic contaminants.
There are various classes of activated carbon, including Powdered Activated Carbon (PAC), Granular Activated Carbon (GAC), and Extrusion Activated Carbon (EAC). PAC is a powdered activated carbon (U.S. mesh size 80) with a particle size of predominantly less than 0.18 mm, while GAC and EAC are granules or cylinders with a particle size between 0.2 and 5 mm. PAC is commonly used in the fields of decolorization, food processing, and medicine. GAC is commonly used in continuous processes for gas and liquid phase applications, while EAC is most commonly used in gas phase applications. Compared with PAC, the GAC or EAC and other molded active carbon has the advantages of reduced pressure, good reproducibility, reusability, high hardness, small abrasion and the like.
In order to improve the adsorption performance of pollutants when treating complex wastewater containing inorganic and organic pollutants, zeolite and activated carbon adsorbent are connected in series to form a mixed adsorbent system for industrial application. The use of such systems results in larger system footprints, increased system costs, and extended processing times. One approach is to combine the zeolite and activated carbon in one adsorbent material system. However, to date, these attempts to form such a combined system have had drawbacks or other difficulties, including high cost, clogging of the adsorbent pore channels with adhesive, low mechanical strength, and the like. Several examples of such combined systems are provided below.
Foo et al in "The Environmental Applications of Activated Carbon/Zeolite composites", Advances in Colloid and interface science, 2011,16222-28, the current common methods for preparing zeolite and activated carbon composite adsorbents are reviewed. The most common method of making zeolite and activated carbon composite adsorbents is to use a previously produced zeolite as one material component and activated carbon or a carbonaceous precursor material (such as an organic polymer) as another material component. Binders are typically used to shape and/or provide mechanical strength to the final sorbent product. The use of pre-produced zeolites and/or pre-produced activated carbon results in high costs for the composite adsorbent.
Boxley et al, in published U.S. patent application US2013/0312668a1, teach a method of making a sorbent material by mixing mixture components comprising a pozzolan, an alkaline activator, and water to initiate a geopolymerization reaction to form a coagulated mixture, and collecting the coagulated mixture as a sorbent. It may further be supplemented with other ingredients including zeolites and activated carbon. Previously prepared zeolite and activated carbon were used to prepare the adsorbent material. Neither zeolites nor activated carbon are generated in situ in the adsorbent material.
Chinese patent application CN101053826A describes a method for preparing geopolymer adsorbent, comprising three components: geopolymer material, solid adsorption media and metal chloride media (such as CaCl)2、SrCl2、MgCl2Etc.). Solid adsorbent media include zeolites and activated carbon. Previously prepared zeolite and activated carbon were used as solid adsorption media to prepare the adsorption material. Neither zeolites nor activated carbon are generated in situ in the adsorbent material.
Jha et al at "Sound Properties of The Activated Carbon-Zeolite compositional From Coal Fly Ash For Ni2+,Cu2+,Cd2+and Pb2+(activated carbon zeolite composite material prepared from fly ash to Ni2+、Cu2+、Cd2+And Pb2+Adsorption performance of) "of Journal of Hazardous Materials, 2008,160148-153, a method for preparing a zeolite and activated carbon composite adsorbent from fly ash containing fly ash and unburned carbon residue is taught. Fusing fly ash and sodium hydroxide, grinding and carrying out hydrothermal treatment to form zeolite. The resulting zeolite and activated carbon composite is therefore in powder form, which is unsuitable for use in a continuous adsorption process for liquid or gas separation applications as compared to shaped adsorbents.
Ma et al in "CO2Adsorption on Zeolite X/Activated Carbon Composites (Carbon dioxide Adsorption on type X Zeolite/Activated Carbon Composites) ", Adsorption, 2012,18503-510, a process for making a zeolite and activated carbon composite using a mixture of kaolinite-rich coal gangue, silica and asphalt powder is taught. Extruding the mixtureFormed into a cylindrical shape and then subjected to a two-step physical activation process at 850 ℃, including carbonization in nitrogen and activation in carbon dioxide. The active sample is hydrothermally treated to form zeolite, and the zeolite-active carbon composite particles are prepared.
Thus, to date, these attempts to form such a combined system have had drawbacks or other difficulties, including: the material cost due to the use of previously produced zeolite and activated carbon is too high, the production cost due to the two-step high temperature physical activation process is too high, the binder blocks the pore channels of the adsorbent, the shape and size of the adsorbent required for a continuous adsorption process are lacking, the mechanical strength is low, and the like. Clearly, a zeolite and activated carbon composite adsorbent formation process that is high performance, low cost, and has desirable shape and size is currently needed.
Disclosure of Invention
To address the adsorption limitations of single zeolite and activated carbon adsorbents in the treatment of complex waste streams containing inorganic and organic contaminants, a new zeolite and activated carbon composite adsorbent material is needed that combines the advantages of single zeolite and activated carbon adsorbents to effectively remove inorganic and organic contaminants. The combination of two adsorption materials with different surface properties and pore structures, such as zeolite and activated carbon composite adsorbents, provides a versatile and effective adsorption solution for the removal of inorganic and organic pollutants from wastewater. A method of achieving such a combined adsorbent material is described.
It is currently desirable to produce a shaped adsorbent with good strength by an efficient shaping process using inexpensive zeolite and activated carbon precursor materials, then to produce activated carbon in situ by a simple one-step chemical activation using an activating agent contained in the mixture components, and then to synthesize the zeolite in situ by hydrothermal treatment to form the shaped zeolite-activated carbon composite adsorbent. The invention discloses a composite adsorbent composition and a production method thereof, wherein the composite adsorbent is prepared from a mixture of a geopolymer material, a carbon-containing material and an alkali active agent through mixing, molding, alkali activation and hydrothermal treatment, and the composite adsorbent is prepared from zeolite and activated carbon, and the shape and size of the composite adsorbent are suitable for adsorption application. In particular, the present invention provides a method of producing a composite adsorbent having a composition of geopolymer, zeolite and activated carbon, comprising:
a. mixing a geopolymeric material, a carbonaceous material and an alkali activator, wherein the solid mass ratio of alkali activator to carbonaceous material is at least 0.25:1, to produce a paste-like mixture, wherein the paste-like mixture has a uniform composition and rheological properties required for shaping,
b. the paste-like mixture is manufactured using common adsorbent forming methods, including granulation or extrusion, to form a granular or pellet composition having a suitable size for the adsorption process,
c. the particle or pellet composition is cured at ambient temperature or by heating as needed to increase strength,
d. chemically activating carbonaceous material in the particulate or pellet composition in an inert gas at a temperature greater than about 400 ℃ using a basic activator present in the composition to generate activated carbon in situ,
e. subjecting the composition to a hydrothermal treatment to convert a portion of the geopolymer to generate zeolite in situ and form the composite adsorbent, and
f. and washing and drying the generated composite adsorbent.
The process provides a composite adsorbent which can effectively remove organic and inorganic harmful compounds in liquid and gas. The requirement of steps (d) and (e) enables the process to provide the composite sorbent as a mixture at low cost, and to provide a single composite sorbent that is easier to use in waste streams, and has lower waste stream treatment costs.
One aspect of the present invention is a mixture composition comprising: a geopolymer material; a carbonaceous material; and a base activator. The solids mass ratio of the alkaline active agent to the carbonaceous material is at least 0.25: 1. This mixture composition allows the mixture to be formed into granules or pellets. Such compositions are produced by geopolymerization at ambient or slightly elevated temperatures to obtain sufficient material strength for further processing to produce the composite adsorbent. The alkali activator included in the mixture composition alkali activates the carbonaceous material at an elevated temperature in an inert atmosphere to generate activated carbon in situ. The geopolymeric material not only provides mechanical strength to the adsorbent, but also can be partially converted under hydrothermal conditions to generate the zeolite in situ, forming a composite adsorbent comprising zeolite and activated carbon.
Another aspect of the present invention is a method for producing a zeolite and activated carbon composite adsorbent by mixing, shaping, alkali activation and hydrothermal treatment to form the mixture composition into a desired shape and size. The geopolymeric material, carbonaceous material and alkali activator are mixed to produce a paste-like mixture of uniform composition and desired rheology for use in the formation of the sorbent. The paste-like mixture is processed using common shaping methods, such as granulation or extrusion, to form granules or pellets of suitable size for the adsorption and separation process. The granules or pellets are chemically activated at elevated temperatures with an alkaline activator contained in the composition to convert the carbonaceous material to activated carbon. The activated particles or pellets are subjected to a hydrothermal treatment to convert at least a portion of the geopolymeric material to zeolite. The prepared zeolite and activated carbon composite adsorbent is washed with deionized water and dried for adsorption applications.
The zeolite and activated carbon composite adsorbents disclosed herein may be used in any application where the use of adsorbents is desired, including liquid and gas adsorption, purification, or other separation applications.
Drawings
Figure 1 illustrates in flow chart form the process steps for making the composite adsorbent of the present invention.
Fig. 2A and 2B show two optical images of different size ranges of composite adsorbent particles of example 1. FIG. 2A shows 10-20 mesh; FIG. 2B shows 20-40 mesh.
Fig. 3A and 3B graphically plot the adsorption performance evaluation breakthrough curves for the adsorbents in example 5 and comparative example a.
Detailed Description
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting. As used in this specification, the singular forms "a", "an" and "the" include plural referents unless the content clearly dictates otherwise. The following terms in the glossary used in the present application are defined below, and for these terms, the singular includes the plural.
Various headings are presented to aid the reader, but are not the only locations in all aspects of the referenced subject matter and should not be construed as limiting the location of such discussion.
Glossary
Ambient temperature means room temperature, typically 20-25 ℃.
Wt% means weight percentage.
Discussion of the related Art
The invention discloses a composition and a preparation process of a composite adsorbent consisting of zeolite and activated carbon, wherein the zeolite and the activated carbon have required shapes and sizes suitable for adsorption application, the composite adsorbent is formed by mixing components of a geopolymer material, a carbonaceous material and an alkali activator, wherein the solid mass ratio of the alkali activator to the carbonaceous material is at least 0.25:1, so as to generate a pasty mixture for molding with uniform composition and required rheological property; processing the paste using conventional adsorbent forming methods (including granulation or extrusion) to form granules or pellets of suitable size for the adsorption process; under an inert gas (e.g. N) at a temperature generally higher than 400 deg.C, preferably in the range of 400-1000 deg.C2) Chemically activating a carbonaceous material with an alkaline activator contained in the composition to generate activated carbon in situ; performing a hydrothermal treatment to convert a portion of the geopolymer to zeolite; the prepared zeolite and activated carbon composite adsorbent is washed and dried for adsorption applications. FIG. 1 illustrates these process steps in a flow chart for making the composite adsorbent of the present invention.
Geopolymers are a class consisting of SiO4And AlO4An aluminum silicate inorganic polymer of an amorphous three-dimensional polysilicate network of tetrahedral composition. The formation of geopolymers involves an aluminosilicate source material and an alkali silicate activator solution. In a typical synthesis, calcined clay or fly ash is mixed with an alkali silicate solution to formA geopolymer. The geopolymerization process includes three phases: 1) dissolving aluminum silicon ions from an aluminosilicate source, and reacting with hydroxide ions to generate a movable monomer; 2) the monomers reorient and align to form larger oligomers; 3) condensation polymerization of oligomers to form oxygen bonded SiO4And AlO4A rigid three-dimensional network of tetrahedrons.
Geopolymeric materials can be cured at room temperature and achieve many excellent material properties, such as high strength as well as thermal and chemical stability. One typical characteristic of geopolymers is their ability to cure and increase the strength of the material at ambient or slightly elevated temperatures after mixing. They have been used in many fields such as construction cement and refractory materials. The geopolymerization process begins when an alkali silicate activator is mixed with an aluminosilicate source material. Geopolymers typically set within a few hours, during which time the mixture forms a rigid polymer network, loses plasticity and hardens, and gains high material strength.
Activated carbon may be made from carbonaceous materials including coal, petroleum coke, biomass, and the like. Due to abundant resource and low cost, biomass waste is increasingly used as a raw material for producing activated carbon. Activated carbon can be prepared by physical or chemical activation methods. The physical activation method mainly comprises two processes of carbonization and water vapor or carbon dioxide activation. Chemical activation is a one-step process carried out in the presence of an activating agent (e.g., alkali hydroxide, phosphoric acid, zinc chloride, etc.). Chemical activation typically occurs at temperatures lower than those required for physical activation (typically greater than 800 ℃). Activated carbon is reported to have a high specific surface area when prepared with an alkali metal hydroxide such as sodium hydroxide as an activator.
In the present invention, it has now been found that mixing a geopolymer material, a carbonaceous material and an alkaline active agent in a ratio of alkaline active agent to carbonaceous material solids of at least 0.25:1 by mass produces a paste-like mixture having a uniform composition and desired rheology, using conventional adsorbent forming methods such as granulation or extrusion, allows the paste-like mixture to be efficiently formed into granules or pellets having a desired shape and size, and allows for sufficient material strength to be obtained in a short period of time by geopolymerization at ambient or slightly elevated temperatures for further processing to produce a composite adsorbent.
The geopolymerization process begins after the geopolymer material is prepared and mixed with the carbonaceous material and the activator to produce a homogeneous paste. Since geopolymer materials typically take several hours to set and harden at room temperature, the paste mixture can be processed into granules using a granulation process, or the granules can be processed into pellets using an extrusion process. After the granules or pellets are formed, they may be cured at room temperature or heated to a temperature typically below 150 ℃ to accelerate curing to develop sufficient material strength for further processing, such as sieving, activation and hydrothermal treatment.
The present invention has now shown that most carbonaceous materials, including coal, petroleum coke, biomass and other materials commonly used in the manufacture of activated carbon, can be processed to smaller particle sizes than granules or pellets, and can be prepared and formed into well-mixed paste-like mixtures with geopolymeric materials. In addition, the biomass material can be premixed with an alkaline activator solution for aging and optionally heated to soften and decompose the biomass material for ease of processing and improved homogeneity. In addition, premixing and aging the biomass material with an alkaline activator solution also increases the extent of alkaline activation of the biomass to produce activated carbon.
For carbonaceous materials such as coal, charcoal and other easily ground materials, they can be conveniently ground to a powder and formed into a homogeneous paste-like mixture with the geopolymer material. For pasty carbonaceous materials such as petroleum asphalt, etc., the carbonaceous materials can be directly mixed with geopolymer materials to prepare uniform mixtures. For biomass carbonaceous materials such as wood, the materials can be processed into wood chips, pre-mixed with an alkali activator such as sodium hydroxide solution to decompose the material, or pyrolyzed to form charcoal for grinding. Processing carbonaceous materials into small particles not only improves the homogeneity of the composite material composition, but also enhances the alkali activation and hydrothermal treatment processes to prepare activated carbon and zeolite in the composite adsorbent.
It is advantageous to use an alkaline activator, such as an alkali metal hydroxide, to produce the zeolite and activated carbon composite adsorbent in a solids mass ratio of alkaline activator to carbonaceous material of at least 0.25:1, more preferably at least 0.5:1, and even more preferably at least 1:1 in the mixture composition. Alkali metal hydroxides such as sodium hydroxide not only act as activators to chemically convert carbonaceous materials to activated carbon, but also provide the necessary alkali component for efficient conversion of geopolymers to zeolites. Furthermore, the addition of alkali metal hydroxide activators aids in the dissolution of the aluminosilicate material in the geopolymer composition, improving the geopolymerization process.
The alkali activator may be added as part of the composition of the geopolymer material or may be added in addition to the geopolymer material and carbonaceous material mixture. The alkaline activation of the carbonaceous material in the mixture composition may be carried out in an inert gas (e.g., nitrogen or otherwise) at a temperature above 400 c, typically between about 400 and about 1000 c. It has also been found that base activation also facilitates the conversion of geopolymers to zeolites under hydrothermal conditions.
After the mixture composition is activated by alkali, the activated particles or pellets are subjected to hydrothermal treatment, so that part of the geopolymer can be converted into zeolite. Since the geopolymer is an aluminum silicate material, depending on its composition, the geopolymer can be partially converted to zeolite by hydrothermal treatment in water, alkali solution or other medium. Zeolite hydrothermal synthesis typically involves heating the geopolymeric material to a temperature of about 30 to about 200 ℃ for 1 to 168 hours to produce the desired zeolite. The type of zeolite formed after hydrothermal treatment depends on the composition of the geopolymer and the hydrothermal conditions, including A, X, Y, T, P, beta, mordenite and other zeolites. After hydrothermal treatment, the in-situ generated zeolite and activated carbon composite adsorbent is washed and dried for adsorption applications.
The present invention provides a unique mixture composition and advantageous manufacturing process to produce a high performance, low cost zeolite and activated carbon composite adsorbent having a desired shape and size. The mixture of the composite adsorbent is prepared by using low-cost and abundant geopolymer materials, biomass and other carbon-containing materials, and the zeolite-activated carbon composite adsorbent prepared by using high-cost zeolite and activated carbon as raw materials is replaced. The mixture composition can be conveniently shaped using conventional shaping methods to produce granules or pellets of suitable size and good strength. The use of an alkaline activator in the mixture composition not only provides good material strength for geopolymerization reactions, but also chemically activates carbonaceous materials to activated carbon and facilitates efficient conversion of geopolymers to zeolites to form zeolite-activated carbon composite adsorbents.
The process may be further understood by reference to the flow diagram of FIG. 1, as follows:
the geopolymer material according to step 1 of figure 1 may be prepared by mixing an aluminosilicate source material, an alkali-activated material and a carrier fluid. The general formula of the geopolymer is Mn[-(SiO2)z-(AlO2)-]nWherein M is monovalent cation, z is silicon-aluminum ratio, and n is polymerization degree. M is typically an alkali metal such as lithium, sodium, potassium or other monovalent cation, and z is typically 1, 2, 3 or up to 32. The geopolymer material may be prepared using any suitable composition defined by the general formula of the geopolymer.
The geopolymer composition according to step 1 of fig. 1 typically comprises an aluminosilicate source. Exemplary aluminosilicate materials include, but are not limited to, metakaolin, calcined kaolin clay, fly ash, blast furnace slag, alumino-silica fume, and the like. The source of aluminosilicate is preferably metakaolin, calcined clay, fly ash, slag or a combination of two or more such materials.
The geopolymer composition according to step 1 of fig. 1 typically comprises an alkali silicate activator. The alkali silicate activator generally comprises an alkali or alkaline earth metal silicate component. Reference herein to "alkali" compounds is intended to refer to alkali metal (e.g., Li, Na, and K) and alkaline earth metal (e.g., Mg, Ca) compounds. The alkali silicic acid component comprises at least one of sodium silicate, potassium silicate, lithium silicate, calcium silicate, or magnesium silicate. The alkali silicic acid component preferably comprises sodium silicate.
The geopolymer composition according to step 1 of figure 1 typically comprises a carrier fluid. The carrier liquid may be water, an organic solvent, other liquid, or a combination of two or more liquids. The carrier liquid is preferably water. The geopolymer component is considered to be already present in the carrier fluid if the aluminosilicate source or metal hydroxide activator is already in the liquid state.
The carbonaceous material according to step 1 of fig. 1 is a material containing a large amount of carbon. Examples of carbonaceous materials include coal, petroleum coke, pitch, wood, bamboo, coconut shells, lignite, rice hulls, waste rubber tires, and the like. Depending on the nature of the carbonaceous material, they may be used directly in admixture with the geopolymer material, ground or pyrolyzed prior to grinding to obtain a powder form, or the decomposed material may be pretreated with chemicals such as alkali hydroxides to facilitate processing.
The alkali activator according to step 1 of fig. 1 typically comprises an alkali or alkaline earth metal hydroxide or salt typically used for chemical activation to produce activated carbon. The alkali hydroxide component includes at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide, and the like, preferably sodium hydroxide. The solids mass ratio of alkali activator to carbonaceous material in the mixture composition is preferably at least 0.25:1, more preferably at least 0.5:1, even more preferably at least 1: 1. The alkali activator may be added as part of the composition of the geopolymeric material or in addition to the geopolymeric material and carbonaceous material mixture.
The sorbent forming process according to step 2 of fig. 1 includes granulation, extrusion and other sorbent manufacturing processes. Adsorbent granulation processes, such as wet granulation, dry granulation, spray drying, and the like, are commonly used to produce adsorbent particles. Extrusion processes are commonly used to produce cylindrical or other shaped sorbent pellets.
The curing of the composition according to step 3 of fig. 1 may be carried out at ambient temperature or by increasing the temperature of the mixture composition by providing a heat source. Heating may be achieved by convection, radiation or conduction methods. Curing may be carried out at a temperature of from about 20 ℃ to about 150 ℃, preferably between about 40 ℃ to about 100 ℃, more preferably between about 50 ℃ to about 80 ℃. Curing of the geopolymer composition may generally be carried out for between 1 and 72 hours, preferably between about 4 and about 48 hours, and more preferably around about 8 to 24 hours. Curing of the mixture composition may be carried out in the presence of air, moisture, steam, fumes, water, solvents, or other gases or liquids. Most preferably, the curing is carried out in the presence of moisture, water or steam.
The alkali activation of the carbonaceous material in the mixture composition according to step 4 of fig. 1 may be carried out in an inert gas (e.g., nitrogen, argon, helium, or others) in the presence of an alkali activator, typically at a temperature of between about 400 ℃ and about 1000 ℃, preferably between about 500 ℃ and about 900 ℃, more preferably between about 600 ℃ and about 800 ℃ to produce activated carbon. Optionally, the treatment can be carried out in carbon dioxide, steam or other gas to further improve the performance of the activated carbon.
Hydrothermal treatment of the active mixture composition according to step 5 of fig. 1 is achieved by heating in a hydrothermal treatment medium at a temperature necessary to convert at least a portion of the geopolymer to zeolite. Depending on the type of geopolymer composition and the type of zeolite desired, the hydrothermal treatment is generally carried out at a temperature of less than about 250 ℃, advantageously less than about 200 ℃, preferably less than about 150 ℃ and in the range of about 40 to about 150 ℃, most preferably in the range of about 60 to about 120 ℃. The hydrothermal treatment time is generally between 1 and 168 hours, preferably between 1 and 72 hours, more preferably between 2 and 48 hours, even more preferably between 4 and 24 hours.
The invention will be further clarified by a consideration of the following examples, which are intended to be purely exemplary of the invention.
Materials and equipment:
the activated Carbon adsorbent is Filtrasorb 300, available from Calgon Carbon, Moon Township, Pa
h represents hour
L represents L
The metakaolin is PowerPozz metakaolin purchased from Advanced ceramic Technologies, Blaine, WA
meq means milliequivalents
ppm means parts per million
The sodium silicate solution is grade 40 purchased from Occidental Chemical Corporation, Dallas, TX
Sodium hydroxide is 50% membrane caustic soda purchased from Occidental Chemical Corporation, Dallas, TX
The zeolite adsorbent was 13X zeolite beads available from UOP, Des plants, IL
Example 1
Wood chips and sodium hydroxide activator solution were mixed and aged at room temperature overnight, metakaolin and sodium silicate activator solution were mixed to prepare a geopolymer composition, and then the two mixtures were mixed immediately after the preparation of the geopolymer to prepare a uniform paste mixture to prepare a composite mixture composition. The composite mixture comprised, by weight, 22 wt% metakaolin, 13 wt% sodium silicate solution, 22 wt% dry wood chips, and 43 wt% sodium hydroxide activator solution. The mass ratio of alkali activator (sodium hydroxide solid) to carbonaceous material (wood chips) solid was 1: 1.
The prepared composite paste mixture was ground in a coffee grinder, and then the mixture was shaped and formed into green embryo particles by rotating in a rotating drum. The green embryo particles are placed in a sealed container and heated at 60 ℃ to cure the geopolymer component and further treat the woody material in the particles with an alkali activator. The cured pellets were transferred to a furnace and heated at 700 ℃ for 1h under nitrogen to activate the wood material in the pellets with the contained alkali hydroxide to produce activated carbon. The activated particles were hydrothermally treated in 1mol/L sodium hydroxide solution at 75 deg.C for 24 hours to form a zeolite. After hydrothermal treatment, the resulting particles were washed with deionized water and dried at 120 ℃ for adsorption applications. Fig. 2 shows optical images of composite adsorbent particles made in this example in the size range of 10-20 mesh (fig. 2A) and 20-40 mesh (fig. 2B).
After drying, the composite particles were ground into a powder and subjected to X-ray diffraction (XRD) to characterize the crystalline phase of the material. The composite material contains NaX and NaA molecular sieves and takes NaX as a main phase, which shows that the geopolymer zeolite forms zeolite after hydrothermal treatment.
To evaluate the inorganic adsorption performance, 0.1g of 20-40 mesh composite particles was added to 100 ml of 200ppm copper sulfate solution and shaken at 100rpm for 24 hours. Post-experiment filtration of the copper solution and analysis of its Cu using a photometer system2+And (4) concentration. Composite adsorbent pair Cu2+Has an adsorption capacity of 39meq/100g (meq/100g), which is higher than that of the commercial zeolite particles (UOP, desplatees, the 13X zeolite beads for IL having an adsorption capacity of 28meq/100g) and activated Carbon particles (Calgon Carbon, MoontTownship, Filtersorb 300 for PA having an adsorption capacity of 14meq/100 g).
To evaluate the organic adsorption performance, 0.1g of 20-40 mesh composite particles was added to a 500ppm phenol solution and shaken at 100rpm for 24 hours. The filtrate was analyzed for phenol concentration using gas chromatography. The adsorption capacity of the composite adsorbent to phenol was 59mg/g, which was higher than that of commercial zeolite particles (UOP, Des Plaines, 13X zeolite particles for IL: 5mg/g), but lower than that of commercial activated Carbon particles (Calgon Carbon, Moon Township, Pa., Filtrasorb 300: 189 mg/g).
Example 2
Wood chips and sodium hydroxide activator solution were mixed and aged at 60 ℃ overnight, metakaolin and sodium silicate activator solution were mixed to prepare a geopolymer composition, and then the two mixtures were mixed immediately after the preparation of the geopolymer to prepare a uniform paste mixture to prepare a composite mixture composition. The composite mixture comprises 15 wt% metakaolin, 9 wt% sodium silicate solution, 22 wt% dry wood chips and 54 wt% sodium hydroxide activator solution by weight. The solids mass ratio of alkali activator (sodium hydroxide solids) to carbonaceous material (wood chips) was 1.2: 1.
The prepared composite paste mixture was treated using the same forming, alkali activation and hydrothermal processes as in example 1. XRD analysis shows that the composite material contains NaX and NaA molecular sieves and takes NaX as a main phase. The inorganic and organic adsorption performance tests of the composite adsorbent were the same as the adsorption test in example 1. Composite adsorbent pair Cu2+The amount of adsorbed phenol (2) was 45meq/100g, and the amount of adsorbed phenol was 71 mg/g.
Example 3
Wood chips are mixed with a sodium hydroxide activator solution, metakaolin is mixed with a sodium silicate activator solution to prepare a geopolymer mixture, and then the two mixtures are mixed immediately after the preparation of the geopolymer to prepare a uniform paste mixture to prepare a composite mixture composition. The composite mixture consisted by weight of 27 wt% metakaolin, 16 wt% sodium silicate solution, 14 wt% dry wood chips and 43 wt% sodium hydroxide activator solution. The solids mass ratio of alkali activator (sodium hydroxide solids) to carbonaceous material (wood chips) was 1.5: 1.
The prepared composite paste mixture was treated using the same forming, alkali activation and hydrothermal processes as in example 1. XRD analysis shows that the composite material contains NaX and NaA molecular sieves and takes NaX as a main phase. The inorganic and organic adsorption performance tests of the composite adsorbent were the same as the adsorption test in example 1. Composite adsorbent pair Cu2+The amount of adsorbed phenol (2) was 27meq/100g, and the amount of adsorbed phenol was 30 mg/g.
Example 4
Mixing and aging wood chips and charcoal powder with a sodium hydroxide activator solution, mixing metakaolin with a sodium silicate activator solution to prepare a geopolymer, and immediately mixing the two mixtures after the preparation of the geopolymer to prepare a uniform pasty mixture to prepare a composite mixture composition. The composite mixture consists of 13 wt% of metakaolin, 8 wt% of sodium silicate solution, 16 wt% of dry wood chips, 8% of charcoal powder and 55 wt% of sodium hydroxide activator solution. The solid mass ratio of the alkali active agent (solid sodium hydroxide) to the carbonaceous material (wood chips and charcoal powder) was 1.1: 1.
The prepared composite paste mixture was treated using the same forming, alkali activation and hydrothermal processes as in example 1. XRD analysis of the prepared composite adsorbent shows that NaX and NaA molecular sieves are formed in the composite material. The inorganic and organic adsorption performance tests of the composite adsorbent were the same as the adsorption test in example 1. Composite adsorbent pair Cu2+The amount of adsorbed phenol (2) was 37meq/100g, and the amount of adsorbed phenol was 79 mg/g.
Example 5
The geopolymer component is prepared by mixing metakaolin with a premixed sodium silicate and sodium hydroxide activator solution, and then mixing the geopolymer with wood chips to prepare a uniform paste mixture. The composite mixture comprises 18 wt% metakaolin, 10 wt% sodium silicate solution, 18 wt% dry wood chips and 54 wt% sodium hydroxide activator solution by weight.
The prepared composite paste mixture was processed by the same molding, alkali activation and hydrothermal processes as in example 1, but at an alkali activation temperature of 750 ℃. XRD analysis of the prepared composite adsorbent shows that zeolite NaX and sodalite are formed. The composite adsorbent was calcined in air at 850 c to determine the carbon content, which was about 20 wt%. Evaluation of inorganic and organic adsorption Properties fixed bed breakthrough curve analysis was performed using 2.5g of 20-40 mesh composite particles. A test column with an inner diameter of 1cm was used. Using a reactor containing 400ppm Cu2+And 1000ppm phenol at a flow rate of 1 mL/min. The effluent sample was analyzed to determine at a given time (C)t) The concentration of the effluent pollutants. By using the concentration (C) of the effluent pollutantst) With influent water contaminant concentration (C)0) The time ratio of (d) was plotted against the penetration curve.
In this example Cu2+And the adsorption breakthrough curve of phenol on the composite adsorbent are shown in fig. 3. Cu2+The adsorption breakthrough curve on the composite adsorbent (fig. 3A) indicates that the composite adsorbent is more effective in removing inorganic contaminants and has a greater adsorption capacity than the mixed activated carbon and zeolite adsorbent of comparative example a. The adsorption breakthrough curve of phenol on the composite adsorbent (fig. 3B) illustrates that the organic adsorption effect and capacity of the composite adsorbent is close to that of the activated carbon and zeolite mixed adsorbent system of comparative example a.
Comparative example A
In order to treat complex wastewater containing inorganic and organic pollutants and improve the adsorption performance of the pollutants, a mixed adsorption system formed by connecting zeolite and activated carbon in series is adopted in industrial application. Since in example 5, about 20 wt% of carbon was present in the composite adsorbent, a mixed adsorbent system comprising 20 wt% of activated carbon adsorbent and 80 wt% of zeolite adsorbent was used to compare the fixed bed adsorption performance of the composite adsorbent with that of the mixed adsorbent system. In each test, 2.5g of mixed adsorbent was used, and the test conditions were the same as those used in example 5. In this example Cu2+And phenol on the mixed adsorbent, the breakthrough curves are shown in fig. 3A and 3B.
Comparative example B
To evaluate the feasibility of using a mixture of geopolymeric material, carbonaceous material and ex situ prepared, pre-synthesized zeolitic material for high temperature alkali activation of in situ prepared activated carbon to prepare a zeolite and activated carbon composite adsorbent, a composite paste mixture containing the pre-synthesized zeolitic material was prepared using a commercial zeolite powder in place of a portion (up to 20%) of the metakaolin material used in example 5, while keeping the other material components the same. The composite paste containing zeolite is treated by the same forming, curing and alkali activation processes.
XRD analysis of the cured composite material revealed that the mixture contained zeolite NaX and amorphous geopolymer material, indicating that the mixture contained zeolite NaX. However, after alkali activation of the cured mixture in nitrogen at 750 ℃ to activate the wood material in the mixture to produce activated carbon, XRD analysis of the activated composite mixture showed that no zeolite phase was present in the mixture, indicating that the incorporated zeolite NaX had been destroyed by the alkali activation process of the carbon. Thus, the use of a mixture of geopolymeric material, carbonaceous material and ex situ generated, pre-synthesized zeolite material to generate in situ activated carbon by alkali activation at elevated temperatures does not generate zeolite and activated carbon composite adsorbents.
Although the present invention has been described with reference to preferred embodiments thereof, one of ordinary skill in the art, upon reading and understanding the present specification, will appreciate that changes and modifications may be made without departing from the scope and spirit of the invention as described above or below. Accordingly, this description is to be construed as illustrative only and is for the purpose of teaching those skilled in the art the general manner of carrying out the invention.
Claims (18)
1. A method of producing a composite adsorbent having components of geopolymer, zeolite and activated carbon, comprising:
(a) mixing a geopolymeric material, a carbonaceous material and an alkali activator, wherein the alkali activator to carbonaceous material solids mass ratio is at least 0.25:1, to produce a paste-like mixture, wherein the paste-like mixture has a uniform composition and rheological properties required for shaping,
(b) the paste-like mixture is manufactured using common adsorbent forming methods, including granulation or extrusion, to form a granular or pellet composition having a suitable size for the adsorption process,
(c) curing the particle or pellet composition at ambient temperature or by heating as needed to increase strength,
(d) chemically activating carbonaceous material in a particulate or pellet composition in an inert gas at a temperature greater than about 400 ℃ using a basic activator present in the composition to generate activated carbon in situ,
(e) subjecting the composition to a hydrothermal treatment to convert a portion of the geopolymer to generate the zeolite in situ and form the composite adsorbent, and
(f) and washing and drying the generated composite adsorbent.
2. The method of claim 1, wherein the geopolymer material in (a) is an aluminosilicate inorganic polymer having a composition consisting of SiO4And AlO4An amorphous three-dimensional network of tetrahedra.
3. The method of claim 1, wherein the geopolymeric material in (a) comprises an aluminosilicate source, an alkali silicate activator, and a carrier fluid.
4. The method of claim 1, wherein the carbonaceous material in (a) is coal, petroleum coke, charcoal, petroleum pitch, wood, bamboo, coconut shell, lignite, rice hulls, waste rubber tires, or biomass.
5. The process of claim 1, wherein the alkali activator in (a) is an alkali or alkaline earth metal hydroxide or salt.
6. The method of claim 5, wherein the alkali metal hydroxide is at least one of sodium hydroxide, potassium hydroxide, or lithium hydroxide.
7. The method of claim 6, wherein the alkali activator is sodium hydroxide.
8. The process of claim 1, wherein the solids mass ratio of the base activator to carbonaceous material in (a) is at least 0.5: 1.
9. The process of claim 1, wherein the solids mass ratio of the base activator to carbonaceous material in (a) is at least 1: 1.
10. The process of claim 1, wherein the inert gas in (d) is nitrogen.
11. The method of claim 1, wherein the curing in (c) is at a temperature of about 20 to about 150 ℃ for 1 to 72 hours.
12. The method of claim 1, wherein the curing in (c) is performed in the presence of moisture, water, or steam.
13. The process of claim 1, wherein the temperature in (d) is from about 400 to about 1000 ℃.
14. The method of claim 1, wherein the temperature of the hydrothermal treatment in (e) is less than about 250 ℃.
15. A composite adsorbent comprising a mixture of geopolymer, zeolite and activated carbon whenever produced by the method of claim 1.
16. A method of making a composite adsorbent having a geopolymer, a zeolite and activated carbon, comprising the steps of:
(a) chemically activating carbonaceous material in a particulate or pellet composition in an inert gas at a temperature greater than about 400 ℃ using a basic activator present in the composition to generate activated carbon in situ, and
(b) subjecting the composition of step (a) to a hydrothermal treatment to convert a portion of the geopolymer to generate the zeolite in situ and form the composite adsorbent.
17. The process of claim 16, wherein the temperature in (a) is from about 400 to about 1000 ℃.
18. The method of claim 16, wherein the temperature of the hydrothermal treatment in (b) is less than about 250 ℃.
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